CN1687258A - Nano dye ink for ink jet printing and preparation method thereof - Google Patents

Abstract

A nano-pigment inkjet printing ink and a preparation method thereof relate to the fields of computer inkjet printing and color inkjet printing. The present invention uses a polymer dispersant to modify the surface of the pigment so that the pigment is stably dispersed in the aqueous medium, and then adds a variety of water-soluble co-solvents to prepare a set of colored inks, including red, blue, yellow, Black four-color ink is widely used in various types of inkjet printers, inkjet printers, and photo machines suitable for water-based inks. This ink has the following characteristics: no blocking nozzle, waterproof, bright color, and light fastness.

Description

A kind of nano dye ink for ink jet printing and preparation method thereof

Technical field

A kind of nano dye ink for ink jet printing and preparation method thereof has related to computer ink-jet printing, color painting field.

Technical background

Along with the development of digitizing technique with popularize, inkjet technology is widely used in every field such as office's file printout, outdoor advertising air brushing, digital photograph are developed and printed, textile inkjet printing.Ink-jet printing ink is the key of inkjet technology, is applied as the master with dye ink at present.Dye ink is easy to preparation, but its light fastness is poor, fades easily under illumination, is difficult to satisfy the prolonged preservation requirement of outdoor advertising, important archives and file.These drawbacks limit of dye ink the development of inkjet technology.

Compare with dye ink, aqueous pigment ink light fastness and color fastness to water increase substantially.Present domestic ink-jet printing ink is used still based on dye ink, and dye molecule will decompose and volatilize under ultraviolet irradiation soon, uses out of doors and just has apparent in view fading in one month.The outdoor ink of the printer widespread usage of weeding out the old and bring forth the new now-just refer to pigment ink grinds to form small-particle to solid pigment, is scattered in the special aqueous solvent.Because of apparent color be solid particulate because pigment itself is water-fast, just solved the water-fast problem of image; Next is under ultraviolet irradiation, and a pigment material bigger than dye molecule size is difficult for decomposing, even the outer field molecular breakdown of particle, internal layer equally can keep color, and can keep does not out of doors generally speaking have obvious shank color more than 1 year.Because of the colorant in the ink is a solid particulate, so the shortcoming of this ink maximum is than being easier to blocking sprayer, the key that therefore prepares paint ink be with the granules of pigments stable dispersion in ink.Because the pigment particles surface polarity is low, is difficult for stable dispersion in water medium, make and when formulate ink, disperse stability problem to be difficult to solve, limited its use.Therefore, must carry out modification to surface of pigments and make certain dispersion agent of pigment particles surface coverage, thereby improve the application performance of pigment.

More about the research report of ink-jet printing dyestuff ink abroad, but domestic fewer, the patent of invention about paint ink at home only has ten remainders at present.Japan's rock is rugged respects Jies, gloomy well and expands a human tackiness agent inclusion pigment material such as son, has prepared the photostabilization ink of particle diameter at 0.001～0.15 m; People such as Taiwan Qian Jiaxin, Shen Yuzhang utilize coating technology to prepare particle diameter less than microcapsule phosphorus delustering pigment/mixed with resin body of 1 micron, prepared a kind of ink-jet printing dyestuff ink that contains phosphorescent pigment, by adding branched diol and cithrol, the rate of drying of ink and the water tolerance of printed product have been improved; Li Huiyong, Zhu Liang etc. pass through the carbon black acidifying, and pulverization process has made the good black ink-jet marking ink of print performance again; She Yixuan, Wang Fuxing add secondary alcohol ethoxylated ester compounds in ink vehicle, prepared waterproof, do not had the dizzy black ink of opening.

Summary of the invention

The purpose of this invention is to provide a kind of nano dye ink for ink jet printing and preparation method thereof, adopt a kind of macromolecule dispersing agent, by surface modification to pigment, make pigment stably be scattered in the aqueous medium, add multiple water soluble organic substance again, prepare a cover color inks, comprised red, blue, yellow, black four chromatic inks, be widely used in ink-jet printer, air brushing machine, the wide format printer of various types of suitable use inks.

Technical scheme of the present invention: a kind of nano dye ink for ink jet printing is mixed by pigment, macromolecule dispersing agent, water-soluble cosolvent, nonionogenic tenside and deionized water and stirring, make the water-based paint ink-jet printing ink through emulsification, high speed pulverization, ink viscosity 2～the 8cP that is prepared, surface tension 25～35mN/m, the equal particle diameter 35～300nm of granules of pigments Z, Zeta potential-20～-40mV, pH value 7～10.

The preparation method of this nano dye ink for ink jet printing, its prescription is: 1-15% pigment, the 0.5-9% high-molecular copolymer, the water-soluble cosolvent of 10-50%, the 0.1-5% nonionogenic tenside, the 25-75% deionized water, by prescription high-molecular copolymer is added alkali, the alkali consumption is the 10-20% of copolymer quality, adds deionized water, and heating is dissolved polymkeric substance fully, be hydrolyzed into water miscible macromolecule dispersing agent, add pigment then, water-soluble cosolvent and nonionogenic tenside stirred 20-50 minute for 500-800 rev/min with stirrer, stirred 30-80 minute for 8000-30000 rev/min with mulser then, pulverized 20-300 minute with sand mill again, regulate the pH value at last behind 7-10,, promptly obtain aqueous pigment ink with the filtering with microporous membrane of 0.5～1 μ m.

At least comprise a kind of median size in the ink at the superfine pigment of 35～300nm, macromolecule dispersing agent, nonionogenic tenside, three to eight kinds of water-soluble cosolvent, deionized water.The present invention uses polyocarboxy acid type macromolecule dispersing agent modified pigment surface, and nano dye is dispersed in the ink particle stabilizedly, and other component has good consistency in this macromolecule dispersing agent and the ink, can reduce the surface tension of ink simultaneously; The present invention also adds multiple water-soluble cosolvent, can improve the ink multinomial performance, reduces the surface tension of ink; Improve the whipability of ink; Increase the ink performance of keeping humidity, prevent that ink is at shower nozzle place conjunctiva; Regulate the viscosity of ink; Improved the print performance of ink effectively.Experiment shows that this ink has following characteristics: blocking sprayer, waterproof, color are not beautiful, fast light.

(1) pigment type that uses in the ink

The black pigment kind has C.I. Pigment black 7, C.I. Pigment black 11; The yellow ultramarine kind has C.I. Pigment Yellow 73 3, C.I. pigment Yellow 12, C.I. pigment yellow 17, C.I. Pigment Yellow 73 23, C.I. pigment yellow 34, C.I. Pigment Yellow 73 42, C.I. Pigment Yellow 73 55, C.I. Pigment Yellow 73 95, C.I. Pigment Yellow 73 100, C.I. Pigment Yellow 73 104, C.I. Pigment Yellow 73 108, C.I. pigment Yellow 12 0, C.I. Pigment Yellow 73 153; The red pigment kind has C.I. Pigment red 1, C.I. Pigment red 2, C.I. Pigment red 5, C.I. Pigment red 7, C.I. Pigment red 23, C.I. pigment red 38, C.I. pigment red 4 8:2, C.I. pigment red 4 8:4, C.I. pigment red 4 9:1, C.I. Pigment red 52:2, C.I. Pigment red 57:1, C.I. Pigment red 63:1, C.I. Pigment red 64:1, C.I. pigment red 81, C.I. pigment Red 88, C.I. Pigment Red 92, C.I. Pigment red 101, C.I. Pigment red 104, C.I. Pigment red 105, C.I. Pigment red 106, C.I. Pigment red 108, C.I. Pigment Red 112, C.I. pigment red 122, C.I. pigment red 123, C.I. pigment red 146, C.I. pigment red 149, C.I. Pigment red 166, C.I. Pigment red 168, C.I. Pigment red 170, C.I. Pigment red 172, C.I. Pigment red 185, C.I. Pigment red 190, C.I. Pigment red 209, C.I. pigment red 21 9; The blue pigments kind has C.I. pigment blue 1, C.I. pigment Blue 15, C.I. pigment Blue 15: 1, C.I. pigment Blue 15: 3, C.I. pigment Blue 15: 4, C.I. pigment Blue 15: 6, C.I. pigment blue 16, C.I. pigment blue 1 7:1, C.I. Pigment blue 56, C.I. Pigment blue 63.

(2) macromolecule dispersing agent used of pigment modification

The macromolecule dispersing agent of the present invention's preparation is the multipolymer of vinyl monomer, and the multipolymer of forming dispersion agent has chemical structural formula as follows:

M in the following formula ₁=H ⁺, Na ⁺, NH ₄ ⁺, K ⁺, R=H, CH ₃, COOH, COOCH ₃, COOCH ₂CH ₃, COOC ₄H ₉, R ₁=H, CH ₃, R ₂=CN, CONH ₂, COOCH ₃, COOCH ₂CH ₃, COOC ₄H ₉, C ₆H ₅

The number-average molecular weight of this dispersion agent is 1000-20000, the consumption 0.5-9% in ink, and suitable pH scope is 5-10.

(3) nonionogenic tenside in the ink

Above-mentioned macromolecule dispersing agent can be used with nonionogenic tenside, and the nonionogenic tenside that uses in the ink can be a polyoxyethylene alkylphenol condenses class: as OP-7, OP-10, OP-15; Polyoxyethylene Fatty Alcohol(C12-C14 and C12-C18) condenses class: as paregal O-10, paregal O-20, paregal O-25, peregal A-20; Polyoxyethylene polyols ether fatty acid ester: as Tween40, Tween60, Tween65, Tween80; The polyoxyethylene ester class of lipid acid: as SG-10, SE-10, OE-15; These tensio-active agents can be used alone, but also also mix together, and the consumption in ink is 0.1-5%.

(4) the water-soluble cosolvent in the ink

Ethanol, n-propyl alcohol, Virahol, propyl carbinol, ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1, the 3-8 kind in 6-hexylene glycol, glycol ether, Triethylene glycol, tetraethylene-glycol, Macrogol 200, poly(oxyethylene glycol) 400, Polyethylene Glycol-600, glycerol, trolamine, tetramethylolmethane, 2-Pyrrolidone, the N-methyl-2-methyl-2-pyrrolidone.

Beneficial effect of the present invention: this ink has following characteristic

(1) the granules of pigments particle diameter of using the macromolecule dispersing agent modification in the ink is deposited the difficult macrobead insolubles that produces in the process less than 300nm, guarantees the ink system long-term stability.

(2) because the adding of cosolvent, surface tension, viscosity, performance of keeping humidity, the lathering property of ink have been adjusted, according to different PRN devices, make the ink miscellany of different surfaces tension force and viscosity, have good print performance, not blocking sprayer, printing is good, and can effectively control the live width of print pattern, reduce the emergence phenomenon, improve printing quality.Be widely used in Hewlett-Packard, ink printer Canon, the multiple PRN devices that are suitable for water-base ink such as Mimaki air brushing machine.

Embodiment

The preparation of embodiment 1 red ink

Get 2g maleic anhydride-methylmethacrylate copolymer ( $\stackrel{\‾}{M_n}=8000\±150,$ Mol ratio maleic anhydride: methyl methacrylate=1: 1), add 0.25g sodium hydroxide, deionized water 56g, heating is dissolved multipolymer fully, the C.I. pigment red 122 that adds 5g then successively, the OP-10 emulsifying agent of 2g, the glycol ether of 15g, the ethylene glycol of lOg, 10g glycerol, stirred 20 minutes for 600 rev/mins with stirrer respectively, 10000 rev/mins of high-speed stirring of mulser 40 minutes, sand mill was pulverized 90 minutes, regulated pH value to 9 with sodium hydroxide at last, with the filtering with microporous membrane of 0.5～1 μ m, promptly obtain the water-based paint magenta red ink.The physical index that this ink is 20 ℃ is as follows: surface tension σ=30.5mN/m, and viscosities il=3.45cP, the equal particle diameter d=105nm of particle Z, Zeta potential ξ=-35.6mV.

The preparation of embodiment 2 yellow inks

Get the 3g styrene-maleic anhydride copolymer, ( $\stackrel{\‾}{M_n}=10000\±150,$ Mol ratio vinylbenzene: maleic anhydride=1.5: 1), add 0.3g potassium hydroxide, deionized water 49g, it is molten that heating is dissolved multipolymer fully, the C.I. Pigment Yellow 73 48, the 1g tween 80 that add 7g then successively, 1 of the N-N-methyl-2-2-pyrrolidone N-of 5g, 5g, the Macrogol 200 of ammediol, 20g, 10g Virahol, respectively with stirrer stir 600 rev/mins 50 minutes, the mulser high speed stirred 60 minutes for 10000 rev/mins, and sand mill was pulverized 120 minutes, regulated pH value to 8 at last, with the filtering with microporous membrane of 0.5～1 μ m, promptly obtain the water-based paint yellow ink.The physical index that this ink is 20 ℃ is as follows: surface tension σ=29.3mN/m, and viscosities il=6.5cP, the equal particle diameter d=130nm of particle Z, Zeta potential ξ=-38mV.

The preparation of embodiment 3 blue inks

Get 1g vinylformic acid-butyl acrylate copolymer ( $\stackrel{\‾}{M_n}=15000\±200,$ Mol ratio vinylformic acid: butyl acrylate=1: 1.2), add 20% ammoniacal liquor 4g, deionized water 57g, heating is dissolved multipolymer fully, the C.I. pigment Blue 15 that adds 4g then successively: 3,2g peregal A-20, the pyrrolidone of the Virahol of 6g, the glycol ether of 20g, 10g, respectively with stirrer stir 500 rev/mins 30 minutes, the mulser high speed stirred 30 minutes for 20000 rev/mins, sand mill was pulverized 80 minutes, regulate pH value to 9 at last,, promptly obtain the water-based paint blue ink with the filtering with microporous membrane of 0.5～1 μ m.The physical index that this ink is 20 ℃ is as follows: surface tension σ=27.5mN/m, and viscosities il=4.35cP, the equal particle diameter d=98nm of particle Z, Zeta potential ξ=-29.6mV.

The preparation of embodiment 4 India inks

Get 5g phenylethylene-maleic anhydride mono-methyl multipolymer ( $\stackrel{\‾}{M_n}=3000\±100,$ Mol ratio vinylbenzene: maleic anhydride mono-methyl=1: 1.5), add 0.5g sodium hydroxide, the 43g deionized water, heating makes the multipolymer dissolving, add the C.I. Pigment black 7 of 13g, the Virahol of 3g SE-10,6g, the glycol ether of 20g, the pyrrolidone of 10g then successively, stirred 20 minutes for 800 rev/mins with stirrer respectively, 15000 rev/mins of high-speed stirring of mulser 40 minutes, sand mill was pulverized 100 minutes, regulate pH value to 8.5 at last, with the filtering with microporous membrane of 0.5～1 μ m, promptly obtain the water-based paint black ink.The physical index that this ink is 20 ℃ is as follows: surface tension σ=33.6mN/m, and viscosities il=3.89cP, the equal particle diameter d=175nm of particle Z, Zeta potential ξ=-25.5mV.

Claims (6)

1. A nano-pigment ink-jet printing ink is characterized in that it is mixed by pigment, macromolecular dispersant, water-soluble co-solvent, nonionic surfactant and deionized water, and is made of water-based pigment ink-jet through emulsification and high-speed pulverization The printing ink has a viscosity of 2-8cP, a surface tension of 25-35mN/m, a Z-average particle diameter of pigment particles of 35-300nm, a Zeta potential of -20--40mV, and a pH value of 7-10. 2. the preparation method of nano pigment inkjet printing ink as claimed in claim 1, it is characterized in that formula is: 1-15% pigment, 0.5-9% macromolecular copolymer, 10-50% water-soluble co-solvent, 0.1 -5% non-ionic surfactant, 25-75% deionized water, add alkali to the polymer copolymer according to the formula, the amount of alkali is 10-20% of the mass of the copolymer, add deionized water, heat to dissolve the copolymer completely , hydrolyzed into a water-soluble polymer dispersant, then add pigments, water-soluble co-solvents and non-ionic surfactants, stir with a mixer at 500-800 rpm for 20-50 minutes, and then use an emulsifier at 8000-30000 rpm Stir for 30-80 minutes, then pulverize with a sand mill for 20-300 minutes, finally adjust the pH value to 7-10, and filter with a 0.5-1 μm microporous membrane to obtain the water-based pigment ink. 3. The preparation method according to claim 2, wherein the pigments used are black pigments including C.I. Pigment Black 7 and C.I. Pigment Black 11; yellow pigments include C.I. Pigment Yellow 3, C.I. Pigment Yellow 12, and C.I. Pigment Yellow 17 , C.I. Pigment Yellow 23, C.I. Pigment Yellow 34, C.I. Pigment Yellow 42, C.I. Pigment Yellow 55, C.I. Pigment Yellow 95, C.I. Pigment Yellow 100, C.I. Pigment Yellow 104, C.I. Pigment Yellow 108, C.I. ;Red pigment varieties include C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 5, C.I. Pigment Red 7, C.I. Pigment Red 23, C.I. Pigment Red 38, C.I. Pigment Red 48:2, C.I. Pigment Red 49:1, C.I. Pigment Red 52:2, C.I. Pigment Red 57:1, C.I. Pigment Red 63:1, C.I. Pigment Red 64:1, C.I. Pigment Red 81, C.I. Pigment Red 88, C.I. Pigment Red 92, C.I. Pigment Red 101, C.I. Pigment Red 104, C.I. Pigment Red 105, C.I. Pigment Red 106, C.I. Pigment Red 108, C.I. Pigment Red 112, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 146, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 170, C.I. Pigment Red 172, C.I. Pigment Red 185, C.I. Pigment Red 190, C.I. Pigment Red 209, C.I. Pigment Red 219; blue pigments include C.I. Pigment Blue 15, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, C.I. Pigment Blue 16, C.I. Pigment Blue 17:1, C.I. Pigment Blue 56, C.I. Pigment Blue 63. 4. preparation method according to claim 2 is characterized in that the structural general formula of polymer dispersant is

In the above formula, M ₁ =H ⁺ , Na ⁺ , NH ₄ ⁺ , K ⁺ , R = H, CH ₃ , COOH, COOCH ₃ , COOCH ₂ CH ₃ , COOC ₄ H ₉ , R ₁ =H, CH ₃ , R ₂ = CN, CONH ₂ , COOCH ₃ , COOCH ₂ CH ₃ , COOC ₄ H ₉ , C ₆ H ₅ , the number average molecular weight of this dispersant is 1000-20000, and the dosage in the ink is 0.5-9%. The pH range is 7-10. 5. The preparation method according to claim 2, wherein the water-soluble co-solvent used comprises ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, 1,3-propylene glycol, 1,4-butane Diol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, Three to eight of glycerol, triethanolamine, pentaerythritol, 2-pyrrolidone, and N-methyl-2-pyrrolidone. 6. preparation method according to claim 2 is characterized in that used nonionic surfactant comprises polyoxyethylene alkylphenol condensate: OP-7, OP-10 or OP-15; Polyoxyethylene fatty alcohol condensate : Pingpingjia O-10, Pingpingjia O-20, Pingpingjia O-25 or Pingpingjia A-20; polyoxyethylene polyol ether fatty acid ester: Tween40, Tween60, Tween65 or Tween80; polyoxyethylene ester of fatty acid: SG-10, SE-10 or OE-15; the nonionic surfactant used is one or more of the above nonionic surfactants.